Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
  • B01D53/8621—Removing nitrogen compounds
  • B01D53/8625—Nitrogen oxides
  • B01D53/8628—Processes characterised by a specific catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/86—Catalytic processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/889—Manganese, technetium or rhenium
  • B01J23/8892—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/54—Nitrogen compounds
  • B01D53/56—Nitrogen oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/889—Manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/024—Multiple impregnation or coating
  • B01J37/0242—Coating followed by impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/024—Multiple impregnation or coating
  • B01J37/0244—Coatings comprising several layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/206—Rare earth metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/2073—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20746—Cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/402—Dinitrogen oxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/55—Cylinders or rings
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/30—Improvements relating to adipic acid or caprolactam production

Definitions

• the present invention relates to a catalyst for the catalytic decomposition of nitrogen protoxide (N 2 0) to nitrogen and oxygen, and to its use for the removal of the protoxide from gas mixtures which contain it, particularly for removing the emissions of nitric acid and adipic acid plants.
• N 2 0 nitrogen protoxide
• Nitrogen protoxide is a harmful greenhouse gas that is much more powerful than carbon dioxide; moreover, in the stratosphere it takes part in the reactions that lead to the destruction of the ozone layer.
• the main industrial sources for the formation of nitrogen protoxide are plants for the production of nitric acid and adipic acid (monomer used in the preparation of nylon 6,6 and 6,12).
• Nitrogen protoxide is present in the emissions of adipic acid plants in considerable amounts: a typical composition comprises, in percentage by volume: 30% N 2 0, 2% C0 2 , 2.5% H 2 0, 8-12% 0 2 , 50-150 ppm NOx, remainder N 2 .
• the emissions of nitric acid plants generally contain 300-1700 ppm of N 2 0, 100-2000 ppm of NO x , 1-4% 0 2 , and nitrogen as the remainder.
• N 2 0 emission from nitric acid and adipic acid plants is expected to grow by approximately 16% in the period 2005-2020.
• catalysts used for the decomposition of N 2 0 are known.
• the main ones are constituted by noble metals supported on metallic oxides of different kinds, zeolites substituted with transition metal ions or on which metal oxides and anionic clays are supported, such as for example hydrotalcites constituted by mixed hydroxides with stratified structure, in which anions of different kinds, exchangeable or not, and water molecules are inserted between two layers.
• Catalysts are known (US 5,705,136) which are constituted by oxides such as MnO, CuO, NiO and CoO supported on MgO, CaO, ZnO, Ti0 2 , Al 2 0 3 -ZnO, Al 2 0 3 -Ti0 2 and the like.
• the catalysts Preferably, the catalysts contain CoO supported on MgO.
• Structures of the type of hydrotalcite such as for example Cu 3 Mg 5 Al 2 (OH) 20 CO 3 3H 2 0, Mn 3 Mg 5 Al 2 (OH) 20 CO 3 H 2 O, are also usable.
• the catalysts specified hereinafter have a high catalytic activity in the decomposition of N 2 0 to nitrogen and oxygen, satisfactory thermal stability up to 900 °C and the ability to keep their activity unchanged for long periods of time.
• the stability at high temperatures is in particular provided by the catalysts when supported on alumina, which is a totally unexpected result in view of the away teaching deriving from the US application.
• the catalysts specified hereinafter have the characteristic that they do not contain copper, an element that might have volatility problems in case of reactions conducted at high temperatures, such as for example in the operating conditions for abating of N 2 0 by-product directly in the reactor for oxidation of ammonia to nitrogen monoxide.
• the catalysts comprise mixed oxides of cobalt, manganese and rare earth metals, which are present in the following composition expressed as percentage by weight of CoO, MnO and rare earth metal oxide, wherein the metal is present in the lowest state of valence: MnO 38-56%, CoO 22-30%, 22-32% rare earth metal oxide.
• the preferred rare earth metal oxides are lanthanum and cerium oxides and mixtures thereof.
• a preferred composition contains lanthanum oxide in a quantity of 25-30% by weight expressed as La 2 0 3 .
• the mixed oxides that constitute the active components of the catalysts have the characteristic of being p-type semiconductors in which conductivity increases exponentially as the temperature rises, according to an Arrhenius-like law, and in which the charge vectors are constituted by electron vacancies.
• the lattice oxygen takes part in the oxidation reactions.
• the mixed oxides are used on porous inorganic supports, preferably porous oxides, such as alumina, silica-alumina, titanium dioxide, magnesium oxide.
• Alumina preferably in the gamma form, in the form of micro spheroidal particles with a diameter of 30-80 ⁇ , is the preferred support for reactions performed particularly in a fluid bed.
• the surface area (BET) of the catalyst supported in gamma alumina is generally comprised between 90 and 170 m 2 /g.
• the oxides are preferably present in the support in a quantity of 10-30% by weight.
• supports that have a definite geometric shape, such as cylindrical granules having one or more holes, preferably with three lobes, with through holes which are parallel to the axis of the granule.
• Granule size is 3-10 mm in height and the circumference is comprised between 3 and 10 mm.
• the preferred method consists in impregnating the support with an aqueous solution of a salt of lanthanum or cerium or other rare earth metal or mixtures thereof, followed by drying of the support and then calcination at temperatures preferably between 450 and 600 °C.
• the support thus treated is then impregnated with a solution of a salt of manganese and cobalt, subsequently dried and calcinated at temperatures between 500 and 750 °C.
• Any salt of the above cited metals that is soluble in water can be used; nitrates, formates and acetates are preferred.
• the preferred impregnation method is performed dry, i.e., by using a volume of solution of the salts that is equal to, or lower than, the volume of the pores of the support.
• the decomposition of N 2 0 is conducted at temperatures between 400 and 900 °C.
• the higher temperatures are used as the N 2 0 content increases.
• the preferred temperature is between 700 and 900 °C.
• Space velocities are comprised between 3,000 and 100,000 h "1 .
• the N 2 0 content in the mixtures varies from ppm to percentages by volume of more than 20%.
• the catalyst used in the examples had the following composition, expressed as percentage by weight of:
• CoO 26.3
• the preparation was performed by impregnating gamma alumina with an aqueous solution of lanthanum nitrate La(N0 3 ) 3 .
• the support was then dried at 110 °C and then calcinated at 450 °C.
• the calcinated support was impregnated with an aqueous solution of manganese nitrate (Mn(N0 3 ) 2 ) and cobalt nitrate (Co(N0 3 ) 2 ) and then dried at 120-200 °C and calcinated at 700 °C.
• a volume of solution equal to 100% of the volume of the pores of the alumina was used for impregnation.
• the surface area of the catalyst (BET) was 160 m 2 /g and porosity was 0.40 cmVg.
• the catalyst Prior to the test, the catalyst was ground and screened appropriately.
• the light-off activity of the catalyst i.e., the temperature of the gaseous flow at which the catalyst decomposes 50% of the nitrogen protoxide that is present, and the temperature of total decomposition of the protoxide were selected as main criteria for evaluating the performance of the catalyst being considered.
• results are listed in the table and relate to tests conducted at different N 2 0 concentration both on a fresh catalyst and on a catalyst aged for 3 days at 900 °C in air, so as to simulate a worsening of the reaction conditions.
• Example 1 Example 2
• Example 3 Example 4 conditions Fresh sample Aged sample Fresh sample Aged sample

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